JP2023054516A - Curable composition and applications thereof - Google Patents

Abstract

To provide a curable composition capable of forming a cured product that has excellent water repellency and also enables snow or ice on its surface to easily drop therefrom, and applications thereof.SOLUTION: A curable composition contains a silicone-based resin component (A), a reactive silicone-based oil component (B) having at least one reactive group. The silicone-based resin component (A) is substantially free of a D unit. A content of the reactive silicone-based oil component (B) is 0.03-10 pts.mass relative to 100 pts.mass of the silicone-based resin component (A).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a curable composition capable of forming a cured product excellent not only in water repellency but also in snow and ice dropping properties (property in which snow and ice adhering to the surface easily fall from the surface of the cured film), and uses thereof.

In cold regions with heavy snowfall (heavy snowfall regions, etc.), there is a risk of infrastructure failure or functional deterioration due to snow damage, and snow removal work is carried out to ensure a safe and comfortable living environment. However, the snow removal work requires a lot of labor and is very heavy, especially when the snow is wet snow (wet snow containing a lot of water), making the work more difficult and dangerous. Therefore, there are cases in which it is difficult to remove snow frequently, such as in areas where there are few workers, or when there are many outdoor structures to be targeted, or when they are installed in dangerous places.

Another problem is that snow adheres to road signs, information signs, traffic signals (signal lights), etc., making it difficult to remove the snow, resulting in reduced visibility. For example, in recent years, LED-type traffic lights that use LEDs (light-emitting diodes) as light sources have become popular. A phenomenon called "white light" that is covered is becoming more likely to occur.

Therefore, there is a demand for a technique for preventing snow and ice from accumulating on the surface of a base material (solid surface), and for improving the ability to remove snow and ice so that adhered snow and ice naturally fall off.

Japanese Patent Application Laid-Open No. 2-147688 (Patent Document 1) discloses an anti-icing composition having an anti-icing effect. In the example of Patent Document 1, the anti-icing effect is confirmed by measuring the icing shear breaking strength by applying force to the ice adhered to the surface of the object to peel it off. However, there is no mention of the nature of spontaneous fall.

It should be noted that the anti-icing property (property to prevent snow and ice from adhering to the solid surface) is a property that is significantly different from the snow/ice dropping property (property to allow snow and ice adhered to the solid surface to easily fall off). Are known. On page 96 of "Wettability of Solid Surfaces From Superhydrophilicity to Superhydrophobicity (Kyoritsu Shuppan)" (Non-Patent Document 1), it is stated that "a surface to which snow does not adhere easily is not necessarily a surface to which snow easily falls." Are listed. Furthermore, it is also stated that "snow accretion and snow removal are not necessarily governed by the same factors, but vary greatly depending on surface characteristics (water repellency, hydrophilicity) and snow properties (whether it is wet or dry)." there is

In addition, International Publication No. 2019/039468 (Patent Document 2) discloses a curable composition capable of forming a cured product capable of maintaining an antifouling or protective function for a long period of time. It describes water-based properties and snow/ice-removal promotion functions (snow/ice-removal properties). However, even with the curable composition of Patent Document 2, there are cases where the snow-falling and ice-removing properties are not sufficient.

JP-A-2-147688 WO2019/039468

Chemistry Essentials Series 12 Solid Surface Wettability From Superhydrophilicity to Superhydrophobicity (published by Kyoritsu Shuppan Co., Ltd., December 10, 2014)

In addition, many of the snow damage countermeasure paints are colored even if they are of a grade that is supposed to be transparent, and it has been difficult to achieve a high degree of compatibility between falling snow and ice and visibility of the substrate.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a curable composition capable of forming a cured product having not only excellent water repellency but also good snow and ice falling properties, and uses thereof.

Another object of the present invention is to provide a curable composition capable of forming a cured product excellent in water repellency, snow and ice removal properties and water slippage, and uses thereof.

Still another object of the present invention is to provide a curable composition capable of forming a cured product having good water repellency, snow and ice removal properties, water sliding property and appearance, and having excellent workability (coatability or paintability), and uses thereof. is to provide

Another object of the present invention is to provide a curable composition capable of forming a cured product with excellent durability (weather resistance or light resistance) and uses thereof.

Still another object of the present invention is to provide good workability (coatability or coatability) even when applied (or coated) to various substrates, and to improve the visibility (transparency) of the base. An object of the present invention is to provide a curable composition capable of forming an excellent cured product and its use.

As a result of intensive studies to achieve the above object, the present inventors have found that a silicone-based resin component substantially free of D units and a specific reactive silicone-based oil component having a reactive group are mixed in a specific ratio. The present inventors have found that when a curable composition containing the compound is prepared, the cured product obtained by curing exhibits not only high water repellency but also excellent snow and ice falling properties, thereby completing the present invention.

That is, the curable composition (coating composition or paint composition) of the present invention comprises a silicone resin component (A) and a reactive silicone oil component (B) having at least one reactive group. a sexual composition,
The silicone resin component (A) does not substantially contain D units as siloxane units,
The proportion of the reactive silicone oil component (B) is 0.03 to 10 parts by mass with respect to 100 parts by mass of the silicone resin component (A).

The reactive silicone-based oil component (B) preferably has the reactive group only at one molecular end. Alternatively, it is preferably a silicone oil modified with an alkoxy group (alkoxysilyl group) directly bonded to a silicon atom. Further, the reactive silicone oil component (B) is added to the composition prepared under the following conditions (i) to prepare a dry product (a dry film or a coating film) on a smooth substrate. It is preferable that the surface is a reactive silicone oil that satisfies the following (ii) and (iii).

(i) A composition comprising 1 part by mass of the reactive silicone oil component (B) and 99 parts by mass of an isoparaffinic solvent (ii) A water contact angle of 90° or more (for example, 90 to 120° )
(iii) Water sliding angle of 50 μL of water dripping is 25° or less (eg 1 to 25°)

The curable composition may further contain a curing catalyst (C), and the proportion of the curing catalyst (C) is 0.05 parts by mass or more relative to 100 parts by mass of the silicone resin component (A). It may be less than 20 parts by mass, preferably about 0.1 to 19 parts by mass (eg, 1 to 18.5 parts by mass). In addition, the curable composition may further contain a curing catalyst (C) and a solvent (D), the silicone resin component (A), the reactive silicone oil component (B) and the curing The proportion of the total amount of catalyst (C) may be 9.5% by mass or more with respect to the entire curable composition. The curable composition may be a coating composition for promoting snow and ice. The curable composition is cured to form a cured product, snow is adhered to the surface of the obtained cured product, and the time required for the snow to fall when the temperature is raised from -15 ° C. to 8 to 10 ° C. over 30 minutes. is less than the time taken to remove snow deposited on an untreated substrate, such as an A5052 aluminum alloy plate surface.

The present invention includes a cured product of the curable composition, and also includes a method of producing a cured product by coating the surface of a substrate with the curable composition and curing the resulting coating film. do.

The present invention also includes a composite comprising a base material and a cured film covering the surface of the base material and formed of the cured product. The substrate may be a substrate that forms at least a partial region of an outdoor structure. The outdoor structure may be a road sign, guide sign, billboard, electronic bulletin board, traffic light, street light or lighthouse.

Furthermore, the present invention also includes a method of coating the surface of the substrate with the curable composition to form a cured film, thereby promoting snow and ice falling on the surface of the substrate.

In the present specification and claims, the siloxane unit (or siloxane unit) is a structural unit corresponding to one silicon atom forming a polysiloxane [silicone or organopolysiloxane (siloxane resin or siloxane oligomer) ( units constituting the interior or end of the polysiloxane skeleton), ie, basic units selected from M units, D units, T units and Q units.

In the present specification and claims, "A5052 aluminum alloy plate" is a plate made of A5052 aluminum alloy conforming to JIS H4000.

The curable composition (coating composition or paint composition) of the present invention comprises a silicone resin component (A) substantially free of D units and a predetermined reactive silicone oil component (B) having a reactive group. ) in combination at a specific ratio, it is possible to form a cured product that exhibits not only high water repellency but also excellent snow and ice falling properties. It is also possible to form a cured product that is excellent in water repellency, snow and ice removal properties, and water sliding properties. Furthermore, it not only can form a cured product with good water repellency, snow and ice removal properties, water lubricity and appearance, but also contains a silicone-based component having low surface energy (or low surface tension) as a component for improving water repellency. Even if the coating is applied, it can effectively suppress cissing (dents or pinholes), etc., and is also excellent in workability (coatability or paintability). In addition, a cured product having excellent durability (weather resistance or light resistance) can be formed. In addition, even when applied (or coated) to various substrates, the cured product does not easily impair the visibility of the base due to the effects of blurring (white blur), cracks, repelling (dents or pinholes), etc., and is transparent. Since a cured product having excellent properties can be formed, it can be suitably applied to substrates (or members) that require visibility.

[Curable composition (coating composition or paint composition)]
The curable composition of the present invention contains at least a specific silicone resin component (A) and a specific reactive silicone oil component (B). By containing these components in a specific ratio, the curable composition firmly adheres to the base material (molded article, outdoor structure, etc.) and has excellent water repellency and snow and ice removal properties (especially cured membrane) can be formed. In general, in outdoor applications, durability (weather resistance or light resistance) may be reduced due to the fact that the silicone oil component detaches from the coating film when exposed to light, heat, water, snow, etc. Although it may decrease, the curable composition of the present invention can form a cured product (cured film or coating film) with excellent durability.

(A) Silicone-based resin component The silicone-based resin component (A) is a component that forms a siloxane matrix in the cured product, that is, a resin component (silicone-based resin or silicone-based oligomer component) having siloxane units as main structural units. The ratio of the siloxane unit to the total structural units in the silicone-based resin component (A) is about 100% by mass, and substantially no structural units other than the siloxane unit are contained.

Examples of siloxane units include M units [ ^RM ₃ SiO _1/2 ] (wherein ^RM independently represents a hydrogen atom or an organic group), D units [ ^RD ₂ SiO _2/2 ] (wherein , R ^D independently represent a hydrogen atom or an organic group), T units [R ^T SiO _3/2 ] (wherein R ^T represents a hydrogen atom or an organic group) and Q units [SiO _{4/ 2} ].

The organic groups represented by ^RM , ^RD and ^RT are preferably, for example, optionally substituted hydrocarbon groups (non-reactive organic groups).

Examples of hydrocarbon groups forming organic groups include alkyl groups and aryl groups. Alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group and the like. and C _1-6 alkyl groups. Examples of the aryl group include C _6-20 aryl groups such as a phenyl group, a methylphenyl group (tolyl group), a dimethylphenyl group (xylyl group), and a naphthyl group.

Examples of substituents that the hydrocarbon group forming the organic group may have include halogen atoms such as fluorine atoms. Therefore, the hydrocarbon group having a substituent may be, for example, a fluorinated hydrocarbon group (eg, a fluorinated alkyl group such as a 3,3,3-trifluoropropyl group).

The groups R ^M , R ^D and R ^T are preferably organic groups, especially hydrocarbon groups which may have substituents (for example, alkyl groups such as methyl groups, aryl groups such as phenyl groups, or fluorinated alkyl groups such as 3,3,3-trifluoropropyl groups, preferably alkyl groups or aryl groups), more preferably alkyl groups such as C _1-3 alkyl groups, especially C _{A 1-2} alkyl group (especially a methyl group) is preferred.

In addition, in the M unit and the D unit, the types of three R ^M and two R ^D in the same unit may be the same or different. Further, when two or more M units are included, the type of ^RM in each M unit may be the same or different, and when two or more D units are included, the type of RD in each ^D unit may be the same or different. They may be different, and when two or more T units are included, the type of ^RT in each T unit may be the same or different.

The silicone-based resin component (A) may contain each of these siloxane units alone or in combination of two or more.

The silicone-based resin component (A) has T units and/or Q units as main structural units in order to form branched or three-dimensional network cured products (cured films, coating films, etc.). In particular, when the proportion of T units (especially T units in which R ^T is an alkyl group such as a methyl group) is high, it seems that the snow/ice dropping properties and water slip properties can be effectively improved. Therefore, the proportion of T units (especially T units in which R ^T is an alkyl group such as a methyl group) contained in the silicone resin component (A) should be For example, 50 mol% or more (eg, 60 to 100 mol%), preferably 70 mol% or more (eg, 80 mol% or more), more preferably 90 mol% or more (eg, 95 to 100 mol%). It is particularly preferred that the silicone-based resin component (A) consists essentially of T units.

Also, in the silicone resin component (A), if the proportion of D units (especially D units in which both of the two ^RDs are alkyl groups such as methyl groups) is too high, the snow/ice dropping properties and water sliding properties tend to decrease. is. Therefore, the silicone ^- based resin component (A) may contain D units within a range that does not impair the effects of the present invention. The ratio of D units both of which are alkyl groups such as methyl groups) is, for example, 5 mol% or less (eg, 0 to 3 mol%), more preferably 1 mol% or less (eg, 0 to 0.5 mol%). It may be present, and is particularly preferably substantially free of D units (0 mol %).

Examples of the silicone-based resin component (silicone-based resin or silicone-based oligomer) (A) include various corresponding compounds having an alkoxy group at at least one end (one end or both ends) of the molecule. It may be in a shape or a branched shape. That is, the silicone-based resin component (A) is directly bonded to silicon atoms at the ends of the molecules in order to form a cured product by a curing reaction (condensation reaction, hydrolysis reaction, condensation reaction, etc.) caused by heat and/or moisture. Alkoxy groups (silanol groups) and/or hydrolyzable groups such as alkoxy groups (alkoxysilyl groups) directly bonded to silicon atoms, and moisture curing is possible, so alkoxy groups (alkoxysilyl groups) It is preferred to have

Alkoxy groups directly bonded to silicon atoms include, for example, C _1-6 alkoxy groups such as methoxy and ethoxy groups. These alkoxy groups can be used alone or in combination of two or more. Among these, a C _1-3 alkoxy group such as a methoxy group or an ethoxy group is preferred, a C _1-2 alkoxy group is more preferred, and a methoxy group is most preferred.

The silicone-based resin component (A) may be a silicone-based resin, but it can be moisture-cured at room temperature (no heat treatment for curing is required), and can be used (constructed) in places where fire is strictly prohibited, for example. A silicone-based oligomer (siloxane oligomer) is preferred because it can be used. Although there is generally no clear line between silicone-based resins and silicone-based oligomers, silicone-based oligomers refer to dimers to relatively low-molecular-weight polymers (low-molecular-weight silicone-based resins). . Therefore, in the present specification and claims, the molecular weight (or weight average molecular weight) of the silicone-based oligomer can be selected from a range of, for example, about 200 to 10,000, and the upper limit is, for example, about 8,000 or less (eg, about 7,000 or less). , Preferably it may be about 6000 or less (eg, about 5000 or less), may be about 4000 or less (eg, about 3000 or less), may be about 2000 or less (eg, about 1000 or less), etc. The lower limit is, for example, 300 about 400 or more, preferably about 500 or more. In addition, the molecular weight (or number average molecular weight) of the silicone-based oligomer may be selected from a range of, for example, about 200 to 5,000, and the upper limit may be about 4,000 or less (eg, about 3,000 or less), or about 2,000. The lower limit may be about 300 or more (eg, about 400 or more), preferably about 500 or more. The weight average molecular weight and number average molecular weight may be measured by gel permeation chromatography (GPC) (converted to standard polystyrene).

The silicone-based resin component (A) may be one that cures at room temperature by cross-linking alkoxysilyl groups in the presence of a curing catalyst (C) described below, and is a compound represented by the following average composition formula. may

R ¹ _a Si(OR ² ) _b O _(4-ab)/2
(In the formula, R ¹ and R ² independently represent an alkyl group or an aryl group, a is an average value in the range of 0.4 to 1.7, and b is in the silicone resin component (A). It is a value at which the ratio of the group OR ² is 5% by mass or more).

The dynamic viscosity at 25° C. of the silicone-based resin component (A) may be selected, for example, from a range of about 0.1 to 200 mm ² /s, and the upper limit is 120 mm ² /s or less, preferably 100 mm ² /s. The lower limit may be about 0.5 mm ² /s or more (for example, 20 mm ² /s or more).

Specific examples of the silicone-based resin component (A) include methyl-based silicone alkoxy oligomers and methylphenyl-based silicone alkoxy oligomers. Among these, methyl-based silicone alkoxy oligomers are preferred.

Examples of methyl-based silicone alkoxy oligomers include methyl-based silicone methoxy oligomers produced from methyltrimethoxysilane.

The silicone-based resin component (A) may be a commercially available product, such as KC-89S, KR-515, KR-400, KR-500, X-40-9225 (all manufactured by Shin-Etsu Chemical Co., Ltd.). , US-CF-2403, and SR2402 (both manufactured by Dow Corning Toray Co., Ltd.). These silicone resin components (A) may be used alone or in combination of two or more.

The silicone-based resin component (A) may contain a silicone-based resin component having a D unit within a range that does not impair the effects of the present invention. (manufactured by Shin-Etsu Chemical Co., Ltd.) may be contained, but it is preferable not to contain it.

The ratio of the silicone-based resin component (A) is not particularly limited, but may be selected from a range of, for example, about 1 to 90% by mass with respect to the entire curable composition, and the lower limit is, for example, 10% by mass or more. (e.g., 20% by mass or more), preferably 30% by mass or more, more preferably 35% by mass or more, and the upper limit is, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less ( For example, 45% by mass or less). If the proportion of the silicone-based resin component (A) is too low, repelling or loss of luster (white blur or loss of luster) is likely to occur during application depending on the substrate to which it is applied, and the visibility of the base may decrease. On the other hand, if it is too large, the workability (coatability, paintability) will decrease and the appearance of the cured product will be poor. decrease).

(B) Reactive Silicone Oil Component Reactive Silicone Oil Component (Modified Silicone Oil Component, Reactive Silicone Additive or Reactive Silicone Modifier) As (B), water repellency necessary for the cured product , It is a component that imparts water slipperiness, snow and ice removal, etc., has a repeating structure of siloxane units (polysiloxane skeleton), and optionally has M units, T units, Q units, etc. However, a chain (particularly linear) structure formed mainly of D units is preferred.

As the siloxane units (M units, D units, T units, Q units) of the reactive silicone oil component (B), the same units as those exemplified in the section of the silicone resin component (A), etc. is mentioned. These siloxane units may be contained alone or in combination of two or more.

In the siloxane units of the reactive silicone oil component (B), the groups R ^M , R ^D and R ^T are preferably organic groups, especially hydrocarbon groups which may have a substituent (for example, an alkyl group such as a methyl group, an aryl group such as a phenyl group, or a fluorinated alkyl group such as a 3,3,3-trifluoropropyl group, preferably an alkyl group or an aryl group), more preferably C It is an alkyl group such as a _1-3 alkyl group, and particularly preferably a C _1-2 alkyl group (especially a methyl group).

In addition, in the M unit and the D unit, the types of three R ^M and two R ^D in the same unit may be the same or different. Further, when two or more M units are included, the type of ^RM in each M unit may be the same or different, and when two or more D units are included, the type of RD in each ^D unit may be the same or different. They may be different, and when two or more T units are included, the type of ^RT in each T unit may be the same or different.

The D units in the reactive silicone oil component (B) may, for example, mainly contain D units in which both ^RD are alkyl groups such as methyl groups.

The reactive silicone oil component (B) of the present invention only needs to have at least one reactive group. It is a compound having a reactive group (modifying group) only at the terminal siloxane unit, that is, a one-terminal modified silicone-based oil component. If an unmodified (straight silicone oil) is combined with the silicone resin component (A), there is a risk that snow/ice falling properties, water sliding properties, durability, etc., will be degraded.

The type of the reactive group (modifying group) is not particularly limited, and may be a hydroxyl group (or a hydroxyl group-containing group) directly bonded to a carbon atom. Hydrolysis of hydroxyl groups (silanol groups) directly bonded to silicon atoms, alkoxy groups (alkoxysilyl groups) directly bonded to silicon atoms, etc. More preferably, it has an alkoxy group (alkoxysilyl group) directly bonded to a silicon atom (that is, one-end alkoxy-modified silicone oil is more preferable).

The alkoxy group directly bonded to the silicon atom preferably includes a C _1-2 alkoxy group such as a methoxy group and an ethoxy group, and more preferably a methoxy group. In addition, the number of reactive groups in one molecule of the reactive silicone oil component (B) is not particularly limited. good too.

The dynamic viscosity (unit: mm ² /s) at 25° C. of the reactive silicone oil component (B) may be selected from a range of, for example, about 5 to 1000 (eg, 10 to 800, preferably 15 to 100). , the lower limit may be, for example, 20 or more (e.g., 30 or more), preferably 40 or more, more preferably 50 or more (e.g., 80 or more), and the upper limit is, for example, 500 or less (e.g., 300 or less), preferably may be about 200 or less (eg, 150 or less), more preferably about 100 or less (eg, 80 or less). If the kinematic viscosity is too high, it becomes difficult to prepare the curable composition, and even if it can be prepared, it is difficult to apply during painting, or repelling occurs, resulting in poor workability (coating properties, paintability). may decrease. In the present specification and claims, kinematic viscosity can be measured according to JIS Z 8803:2011 (Viscosity measurement method for liquids, Viscosity measurement method using a capillary viscometer).

Reactive silicone oil (B) is prepared by using a composition (diluted solution) prepared under the following conditions (i), and applying a dry product (or When the coating film) is prepared, the surface of the dried product preferably contains a reactive silicone oil that satisfies the following (ii) and (iii).

(i) A composition (diluted solution) consisting of 1 part by mass of the reactive silicone oil component (B) and 99 parts by mass of an isoparaffinic solvent
(ii) a water contact angle of 3 μL of water dripping is 90° or more (iii) a water sliding angle of 50 μL of water dripping is 25° or less

The isoparaffin-based solvent in the composition (diluent) of (i) may be an isoparaffin-based solvent exemplified in solvent (D) described later, preferably CAS registration number 64741-66-8. .

Further, the dried product of the composition (diluted solution) of (i) is obtained by applying the composition described in the condition (i) on a smooth substrate such as a polycarbonate resin substrate (JIS K 6735 compliant) before drying. It can be prepared by applying a ^conventional coating method, such as using a sponge, and drying for about 24 hours in an atmosphere of room temperature (23 ° C.) and humidity of 50% RH. is preferably prepared according to the method described in the examples below.

The water contact angle (ii) of the dried product (or coating film) obtained in (i) is, for example, 90° or more, preferably about 90 to 120°, and the lower limit is more preferably 95° or more. , more preferably 100° or more, and the upper limit is more preferably about 110° or less, further preferably about 105° or less. If the water contact angle (ii) is too small, the water repellency and snow/ice falling properties of the cured product may deteriorate.

In the present specification and claims, a conventional method can be used for measuring the water contact angle (ii), and the drop amount of water used for measurement is preferably 3 μL. It is measured according to the method described in the water repellency test of the example.

The water sliding angle (iii) of the dried product obtained in (i) above may be, for example, 30° or less (for example, 0 to 25° (or more than 0° and 25° or less)), and the upper limit is preferably is 25° or less (e.g. 23° or less), more preferably 20° or less. 10° or more) or 15° or more (for example, 17° or more). If the water sliding angle (iii) is too large, the cured product may have poor water sliding properties and snow/ice falling properties.

In the present specification and claims, a conventional method can be used for measuring the water sliding angle (iii), and the amount of water used for measurement is preferably 50 μL. It is measured according to the method described in the water slipping test of the example.

The silicone-based oil component (B) may be a commercially available product, such as X-22-170BX (single-end carbinol-modified, manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-170DX (single-end carbinol-modified , Shin-Etsu Chemical Co., Ltd.), X-22-176DX (single-end diol-modified, Shin-Etsu Chemical Co., Ltd.), X-22-176F (single-end diol-modified, Shin-Etsu Chemical Co., Ltd.), X-22-176GX-A (single end diol modified, Shin-Etsu Chemical Co., Ltd.), KR-4000A (single end alkoxy modified, Shin-Etsu Chemical Co., Ltd.), KP-983 (single end alkoxy modified, Shin-Etsu (manufactured by Kagaku Kogyo Co., Ltd.) can be used. These reactive silicone oil components (B) can be used alone or in combination of two or more.

The ratio of the reactive silicone oil component (B) is, for example, about 0.03 to 10 parts by mass (for example, 0.05 to 1.5 parts by mass) with respect to 100 parts by mass of the silicone resin component (A). The lower limit is, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.15 parts by mass or more, and particularly preferably 0.25 parts by mass or more (for example, 0.3 parts by mass or more), most preferably 0.35 parts by mass or more (e.g. 0.4 parts by mass or more), and the upper limit is, for example, 10 parts by mass or less (e.g. 5 parts by mass or less), preferably 2 parts by mass or less (eg, less than 2 parts by mass), more preferably 1.5 parts by mass or less (eg, 1.2 parts by mass or less), particularly preferably 1 part by mass or less (eg, 0.8 parts by mass or less), most preferably is 0.7 parts by mass or less (for example, 0.6 parts by mass or less, preferably 0.55 parts by mass or less, particularly 0.5 parts by mass or less). If the proportion of the reactive silicone oil component (B) is too high, cissing may occur during coating (depending on the coating method, etc.), resulting in reduced workability (coatability, paintability), dents (or There is a risk that appearance defects such as unevenness and pinholes may occur. Conversely, if the proportion of the reactive silicone oil component (B) is too small, there is a risk that water slippage, snow/ice dropping properties, especially slippage properties, will be degraded.

(C) Curing Catalyst The curable composition does not necessarily contain a curing catalyst (C), but preferably contains it at least. The curing catalyst (C) is not particularly limited, for example, as long as it is a catalyst capable of promoting normal temperature curing (moisture curing) of the curable composition, and reacts with moisture in the air to hydrolyze and form an active [metal atom —OH], and a condensation reaction (dehydration or dealcoholization condensation, etc.) between [metal atom —OH] and silicone resin component (A) or reactive silicone oil component (B) to bond [metal atom --O--Si] to promote the formation of siloxane bonds [Si--O--Si].

Examples of the curing catalyst (C) include metal alkoxides, metal chelate compounds, metal carboxylates and the like.

Examples of metal alkoxides include titanium alkoxides [titanium tri-C _1-8 alkoxides such as titanium tributoxide; titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide , titanium tetra-C _1-8 alkoxides such as titanium tetraisobutoxide, titanium tetrapentoxide, titanium tetrahexoxide, titanium tetra(2-ethylhexoxide), etc.], aluminum alkoxides (aluminum triethoxide, aluminum trin -propoxide, aluminum triisopropoxide, aluminum tri-s-butoxide, aluminum tri-n-butoxide, etc. ₎ , zirconium alkoxides (zirconium tetra-n-butoxide, zirconium tetra-n-propoxide, etc.) zirconium tetra C _1-8 alkoxide, etc.), germanium _alkoxide (germanium tetra C 1-8 alkoxide, such as germanium tetraethoxide, etc.), tin alkoxide (tin tetra C _1-8 alkoxide, such as tin tetra n-butoxide, tin tetra t-butoxide, etc. ), hafnium alkoxides (hafnium tetra-C _1-8 alkoxides such as hafnium tetra-2-propoxide and hafnium tetra-t-butoxide), niobium alkoxides (niobium penta-C _1-8 alkoxides such as niobium pentaethoxide), tantalum alkoxides ( tantalum penta C _1-8 alkoxides such as tantalum penta n-butoxide, tantalum penta ethoxide, etc.). These metal alkoxides can be used alone or in combination of two or more.

Among these, titanium alkoxide and aluminum alkoxide are preferable, and titanium tetraalkoxide and aluminum trialkoxide are more preferable. A plurality of alkoxy groups in the metal alkoxide differ in reactivity depending on the number of carbon atoms and the presence or absence of branching. On the other hand, if hydrolysis proceeds too quickly, the stability (or workability) may decrease. Therefore, considering reactivity and stability, among titanium tetraalkoxides, titanium tetra C _2-4 alkoxides such as titanium tetraethoxide, titanium tetraisopropoxide, titanium tetraisobutoxide, titanium tetra-n-butoxide are particularly Among aluminum trialkoxides, aluminum tri-C _2-4 alkoxides such as aluminum triethoxide, aluminum triisopropoxide and aluminum tri-s-butoxide are particularly preferred.

The metal alkoxide may be a commercial product such as D-25 (titanium tetra-n-butoxide, manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of metal chelate compounds include metal chelate compounds in which ligands such as β-diketones, phosphate esters and alkanolamines are coordinated to metals.

β-diketones include, for example, 2,4-pentanedione, 2,4-hexanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-decanedione and 2,4-tridecanedione. 5,5-dimethyl-2,4-hexanedione, 2,2-dimethyl-3,5-nonanedione, 2,2,6,6 _- tetramethyl-3,5-heptanedione C _1-3 alkyl C _3-18 alkanedione such as; aryl C _3-18 alkanedione such as 1,3-diphenyl-1,3-propanedione; 1,3-cyclopentanedione, 1,3-cyclohexanedione cycloalkanediones such as; C _1-3 alkyl acetoacetates such as methyl acetoacetate and ethyl acetoacetate; and aryl acetoacetates such as phenyl acetoacetate.

Phosphate esters include, for example, phosphate alkyl esters such as 2-ethylhexyl phosphate.

Examples of alkanolamine include monoethanolamine, diethanolamine, triethanolamine and the like.

These ligands can be used alone or in combination of two or more. Of these, β-diketones are preferred, and C _3-12 alkanediones such as 2,4-pentanedione are particularly preferred.

The central metal (metal atom) forming the metal chelate compound is not particularly limited, and examples include aluminum, titanium, zirconium, niobium, magnesium, calcium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, Examples include palladium, indium, and tin. These metals can be used alone or in combination of two or more. Among these, aluminum, titanium and zirconium are preferred.

Specific metal chelate compounds include, for example, aluminum chelate compounds [e.g., tris(2,4-pentanedionato)aluminum, tris(ethylacetoacetato)aluminum, bis(ethylacetoacetato)(2,4- pentanedionato)aluminum, etc.], titanium chelate compounds [e.g., tetrakis(2,4-pentanedionato)titanium, tetrakis(ethylacetoacetato)titanium, etc.], zirconium chelate compounds [e.g., tetrakis(2,4-pentane zirconium, tetrakis(ethylacetoacetato)zirconium, etc.], niobium chelate compounds [e.g., tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionatoniobium (IV), etc.], magnesium chelate compounds [e.g. diaquabis(2,4-pentanedionato)magnesium etc.], calcium chelate compounds [e.g. diaquabis(2,4-pentanedionato)calcium etc.], chromium chelate compounds [e.g. -pentanedionato) chromium, etc.], manganese chelates [e.g. diaquabis(2,4-pentanedionato)manganese etc.], iron chelates [e.g. chelate compounds [e.g., tris(2,4-pentanedionato)cobalt, etc.], nickel chelate compounds [e.g., bis(2,4-pentanedionato)nickel, etc.], copper chelate compounds [e.g., bis(2,4 -pentanedionato) copper, etc.], zinc chelate compounds [e.g., bis(2,4-pentanedionato)zinc, etc.], gallium chelate compounds [tris(2,4-pentanedionato)gallium, etc.], palladium chelate compounds [e.g., bis(2,4-pentanedionato)palladium, etc.], indium chelate compounds [e.g., tris(2,4-pentanedionato)indium, etc.], suzuki rate compounds [e.g., bis(2,4-pentane dionato)tin, etc.], etc. These metal chelate compounds can be used alone or in combination of two or more.

Among these are aluminum chelates [such as tris-C _3-8 alkanedionato aluminum such as tris(2,4-pentanedionato) aluminum], titanium chelates [such as tetrakis(2,4-pentanedionato) ) Tetrakis C _3-8 alkanedionato titanium such _as titanium], zirconium chelate compounds [e.g. Aluminum chelate compounds [Tris-C _3-6 alkanedionatealuminum, etc.], titanium chelate compounds [tetrakis(2,4-pentanedionato)titanium, etc., tetrakis C _3-6 alkanedionato titanium, etc.] are more preferred.

The metal chelate compound may be a commercially available product, such as Orgatics TC-401 (65% by mass of tetrakis(2,4-pentanedionato)titanium in 2-propanol, manufactured by Matsumoto Fine Chemicals Co., Ltd.). available.

Also, the metal chelate compound may be an alkoxy group-containing metal chelate compound having an alkoxy group in addition to the ligand. Examples of alkoxy groups include C _1-12 alkoxy groups such as methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, 2-butoxy and 2-ethyl-hexyloxy groups. mentioned. These alkoxy groups can be used alone or in combination of two or more. Among these alkoxy groups, C _1-4 alkoxy groups such as 2-propoxy groups are preferred. Examples of alkoxy group-containing metal chelate compounds include alkoxy group-containing aluminum chelate compounds such as aluminum ethyl acetoacetato diisopropylate, aluminum ethyl acetoacetato dibutoxide, bis(2,4-pentanedionato) bis(2- alkoxy group-containing titanium chelate compounds such as propanolate) titanium;

In metal carboxylates (metal salts of carboxylic acids), examples of carboxylic acids include ethanoic acid (acetic acid), propanoic acid (propionic acid), butanoic acid (butyric acid), pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, Linear C _2-18 aliphatic carboxylic acids such as nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid; 2-methylbutanoic acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 4- branched chain C _4-18 aliphatic carboxylic acids such as methyloctanoic acid and 3,5,5-trimethylhexanoic acid; alicyclic carboxylic acids such as naphthenic acid; These carboxylic acids can be used alone or in combination of two or more. Of these, branched-chain aliphatic carboxylic acids are preferred, and branched-chain C _6-10 aliphatic carboxylic acids such as 2-ethylhexanoic acid are more preferred.

The metal forming the metal carboxylate is not particularly limited, and examples thereof include the metals exemplified as the metal forming the metal chelate compound. The metals can be used singly or in combination of two or more. Carboxylic acids that do not form salts are difficult to condense and cannot accelerate room-temperature curing, so they are not preferable as curing catalysts.

Examples of metal carboxylates include aluminum carboxylate, titanium carboxylate, zirconium carboxylate, niobium carboxylate, magnesium carboxylate, calcium carboxylate, chromium carboxylate, manganese carboxylate, iron Carboxylate, cobalt carboxylate, nickel carboxylate, copper carboxylate, zinc carboxylate, gallium carboxylate, palladium carboxylate, indium carboxylate, tin carboxylate, tantalum carboxylate, etc. be done. These metal carboxylates can be used alone or in combination of two or more.

Among these metal carboxylates, zinc carboxylate, iron carboxylate, cobalt carboxylate, and manganese carboxylate are preferred.

Examples of zinc carboxylates include branched chain C _2-12 aliphatic zinc carboxylates such as zinc acetate and zinc bis(2-ethylhexanoate); and zinc alicyclic carboxylates such as zinc naphthenate. be done. Of these, branched chain C _6-10 aliphatic zinc carboxylates such as zinc bis(2-ethylhexanoate) are preferred.

Examples of iron carboxylates include branched chain C _2-12 aliphatic iron carboxylates such as iron acetate and iron bis(2-ethylhexanoate); alicyclic iron carboxylates such as iron naphthenate. be done. Of these, branched C _6-10 aliphatic iron carboxylates such as iron bis(2-ethylhexanoate) are preferred.

Examples of cobalt carboxylates include branched C _2-12 aliphatic cobalt carboxylates such as cobalt acetate and bis(2-ethylhexanoate) cobalt; alicyclic cobalt carboxylates such as cobalt naphthenate. be done. Of these, branched C _6-10 aliphatic cobalt carboxylates such as cobalt bis(2-ethylhexanoate) are preferred.

Examples of manganese carboxylates include manganese acetate, manganese bis(2-ethylhexanoic acid), and other branched C _2-12 aliphatic carboxylates; and manganese alicyclic carboxylates, such as manganese naphthenate. be done. Of these, branched C _6-10 aliphatic manganese carboxylates such as manganese bis(2-ethylhexanoate) are preferred.

These curing catalysts (C) can be used alone or in combination of two or more, and metal alkoxides, metal chelate compounds and metal carboxylates are preferably used alone. Alternatively, the curing catalyst (C) may be prepared as a catalyst solution dissolved in a solvent to be described later. Among these curing catalysts (C), metal alkoxides and metal chelate compounds are preferred, and titanium-based curing catalysts such as titanium alkoxides and titanium chelate compounds are more preferred.

The ratio of the curing catalyst (C) is, for example, 0.05 parts by mass or more and less than 20 parts by mass (for example, 0.1 to 19 parts by mass, preferably 1 to 18 parts by mass) per 100 parts by mass of the silicone resin component (A). 5 parts by mass), and the lower limit is, for example, 0.3 parts by mass or more (e.g., 0.5 parts by mass or more), preferably 0.6 parts by mass or more (e.g., 0.8 parts by mass). above), more preferably 1 part by mass or more (e.g. 3 parts by mass or more), particularly 5 parts by mass or more (e.g. 8 parts by mass or more), and the upper limit is, for example, 19 parts by mass or less (e.g. 18.5 parts by mass or less) ), preferably 16 parts by mass or less (for example, 14 parts by mass or less), and more preferably about 12 parts by mass or less. If the proportion of the curing catalyst (C) is too small, the water slippage will be reduced and it will be difficult to cure quickly at room temperature. decreases, cracks are likely to occur, and there is a risk of poor appearance (or reduced visibility of the base).

(D) Solvent The solvent (D) is the above-mentioned silicone resin component (A), reactive silicone oil component (B) and curing catalyst (C) [also simply referred to as components (A) to (C)]. There is no particular limitation as long as it is a solvent capable of dissolving and/or dispersing.

Examples of the solvent (D) include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol (or 2-propanol) (eg, C _1-4 alkanol, etc.); ethyl acetate, butyl acetate, methoxybutyl acetate, ethyl ester solvents such as glycol acetate and amyl acetate; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and acetylacetone; isopentane, n-hexane, Paraffinic solvents such as isohexane, n-heptane, isoheptane, n-octane, isooctane, nonane, isononane, decane, isodecane, mineral turpentine; naphthenic solvents such as cyclopentane and cyclohexane; benzene, toluene, xylene, trimethylbenzene, etc. aromatic hydrocarbon-based solvents; petroleum-based solvents such as mineral spirits; These solvents can be used alone or in combination of two or more.

Among these, alcohol solvents (C _2-3 alkanols such as 2-propanol), paraffin solvents [preferably isoparaffin solvents from the viewpoint of workability (coatability, paintability) (e.g., isopentane, isohexane, isoheptane , C _4-12 isoparaffinic solvents such as isooctane, isononane, isodecane, preferably C _7-10 isoparaffinic solvents, etc.)].

Furthermore, the solvent (D) preferably does not substantially contain water from the viewpoint of ensuring stability as a paint. The proportion of water in the composition may be 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and most preferably water-free.

The proportion of the solvent (D) is not particularly limited, and may be appropriately adjusted according to the workability (coatability, paintability) and the desired thickness of the cured film (average thickness or weight after drying). The ratio of the total amount of (A) to (C) (especially the concentration of solids forming the cured product) is, for example, 4 with respect to the entire curable composition (especially the total amount of the components (A) to (D)) ~95% by mass (eg, 9.5% by mass or more), the lower limit is, for example, 4% by mass or more (eg, 8% by mass or more), preferably 10% by mass or more (eg, 20% by mass) above), more preferably 25% by mass or more (e.g., 30% by mass or more), particularly 40% by mass or more, and the upper limit is, for example, 95% by mass or less (e.g., 90% by mass or less), preferably 80% by mass or less ( For example, 70% by mass or less), more preferably 65% by mass or less (eg, 60% by mass or less), particularly 55% by mass or less (eg, 50% by mass or less). If the proportion of the total amount of components (A) to (C) is too small, cissing and gloss blurring (white blurring) are likely to occur during application depending on the substrate to be applied and the surface condition, etc., and the visibility of the base is reduced. resulting in a poor appearance, the transparency of the cured product (or the visibility of the base (substrate)) cannot be ensured, or the workability (coatability, paintability) decreases [e.g., productivity or construction (Painting work takes time)]. Conversely, if it is too large, the workability (coatability, paintability) of the curable composition will decrease, and the thickness of the cured film will tend to be uneven due to rapid drying after coating, or depending on the coating method (for example, If a sponge or a brush is used to apply the coating, traces of the coating are likely to remain, and workability (coating properties, paintability) and visibility of the base may be deteriorated.

(E) Other components The curable composition of the present invention, depending on its use and purpose, may further contain a coloring agent such as a pigment, and applications where transparency (or visibility of the base) is important. It is preferable that the ink does not contain a colorant such as a pigment. In addition, an inorganic pigment and an organic pigment are contained in a pigment. Among these, inorganic pigments are preferable from the viewpoint of weather resistance and the like.

Examples of inorganic pigments include simple metals such as aluminum and silver; metal oxides such as zinc oxide, aluminum oxide, chromium oxide, titanium oxide ( _{TiO 2} ), iron oxide [iron oxyhydroxide (FeOOH), etc.]; O ₄ , Cu(Cr, Mn) ₂ O ₄ , Cu(Fe, Mn) ₂ O ₄ , Co(Fe, Cr) ₂ O ₄ , CoAl ₂ O ₄ , Co ₂ TiO ₄ , etc. Metal composite oxide; pearl mica (Pigments obtained by coating a metal oxide such as titanium oxide or tin oxide on natural mica or synthetic mica). These inorganic pigments can be used alone or in combination of two or more. Among these, metal oxides and metal composite oxides are preferred.

The shape of the pigment may be granular, plate-like, scale-like, or the like. The average particle size of the pigment is, for example, 0.01-500 μm, preferably 0.1-200 μm, more preferably 0.5-100 μm, and most preferably 1-10 μm.

When a pigment is contained, the proportion thereof can be appropriately selected depending on the color development property and hiding property of the cured product (cured film), and is 30% by mass or less, for example, about 0.1 to 10% by mass in the curable composition.

The curable composition of the present invention may further contain conventional additives. Usual additives include, for example, antifouling agents (e.g., cuprous oxide, organotin compounds, thiocarbamates, etc.), stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), plasticizers, electrifying agents, Inhibitors, flame retardants, dispersants, surfactants, fillers, viscosity modifiers, preservatives, antifungal agents, antibacterial agents, leveling agents and the like. The total proportion of conventional additives may be up to 30% by weight in the curable composition, eg about 0.1 to 10% by weight.

[Method for preparing curable composition]
The method for preparing the curable composition (coating composition) of the present invention may be a method of mixing the above-described specific silicone resin component (A) and specific reactive silicone oil component (B) in a predetermined ratio. For example, it may be prepared as a one-component curable composition, or from the viewpoint of storage stability, it may be prepared as a two-component curable composition.

When preparing a one-component curable composition, for example, at least a silicone resin component (A) and a reactive silicone oil component (B), and optionally a curing catalyst (C), a solvent (D) and The other ingredients (E) are blended in the absence of moisture (humidity) in the air. Specifically, each component may be blended and mixed under an inert gas atmosphere such as nitrogen gas, and the mixture may be sealed in a container. When a pigment is blended as the other component (E), the pigment may be dispersed in an organic solvent in advance and mixed when blending with other components. The obtained one-component curable composition is usually applied to the substrate (or object) after opening the container at the application site immediately before use.

When preparing a two-component curable composition, the method of separating the two components is not particularly limited, and storage stability and the like are taken into account according to the type of each component [eg, components (A) to (E)]. However, it may be prepared by dividing it into two liquid compositions as appropriate. For example, when using at least components (A) to (D), the silicone resin component (A) and the reactive silicone oil component (B) are mixed to prepare a silicone composition (first liquid composition). Alternatively, the catalyst (C), solvent (D), and optionally other component (E) may be mixed separately to prepare a catalyst composition (second liquid composition). When a pigment is blended as the other component (E), it may be dispersed in advance in an organic solvent and blended in the same manner as in the one-liquid type curable composition. The two-component curable composition thus prepared is usually mixed with the silicone composition and the catalyst composition at the application site to prepare the curable composition for application.

[Use of curable composition]
The curable composition of the present invention can be used as various coating compositions (especially a snow damage countermeasure coating composition for promoting snow and ice falling). For example, the surface of a substrate is coated with the curable composition of the present invention. By curing and forming a cured product (cured film, coating film or protective film), not only water repellency but also snow and ice falling properties can be imparted to the substrate.

The cured product may be a cured film that covers at least the surface of the substrate, or a cured product that has permeated the interior of the substrate. A part of the cured product may form a cured film covering the surface of the base material, and the remaining part may penetrate into the inside of the base material to form a cured product. For example, the curable composition of the present invention is coated on the surface of the object to be protected, which is a base material, and cured to form a protective film. make it easier to fall (promote snow and ice falling).

Therefore, the present invention provides a method of coating the surface of a substrate with the curable composition to form a cured film to promote snow and ice falling on the surface of the substrate; It also includes a composite covering a surface and including a cured film formed from the cured product.

The material of the base material is not particularly limited, and examples include organic materials such as resins (e.g., transparent resins such as methyl methacrylate resins and polycarbonate resins), ceramics (glass, etc.), metals (aluminum or its alloy, stainless steel, etc.).

In addition, the surface of the base material may be treated with various functions such as adhesiveness, colorability (design, decorativeness or aesthetics), hard coat properties, durability, waterproofness, antifouling properties, etc., as necessary. A functional layer (coating film, film or treated surface) may be formed. These functional layers may be formed singly or in combination of two or more. A representative functional layer includes an adhesive layer for enhancing adhesion between the substrate surface and the cured product (cured film or topcoat layer (outermost layer)) of the present invention. For example, the substrate (especially resin substrate) may have an adhesive layer (primer layer) formed of a primer or the like on the surface. The primer is not particularly limited as long as the adhesion between the base material surface and the cured product (adhesion between the base material and the primer layer and between the primer layer and the cured film (topcoat layer)) can be secured, and the type of base material etc. Conventional primers can be used accordingly. The primer layer is not always necessary, and the surface of the base material can be roughened (for example, by blasting) to form a treated surface (or surface treatment layer) such as an uneven surface to improve adhesion with the cured product. good too.

From the viewpoint of effectively exhibiting the effects of the present invention, the curable composition is preferably applied to a base material (member) that forms at least a partial region of an outdoor structure. Examples of outdoor structures include structures or buildings installed outdoors [buildings, storage tanks, bridges, utility poles, cables, antennas, signs or signboards (road signs, information signs, etc.), signboards, electronic bulletin boards , traffic lights (traffic lights, especially LED traffic lights), street lamps, lighthouses, etc.], transportation equipment used outdoors (automobiles, vehicles, ships, aircraft, etc.), preferably covers or housings used for said transportation equipment [e.g. , lights (or lamps), sensors (vehicle-mounted sensors, railcar speedometers, etc.) and other electric/electronic component covers or housings]). Among them, since it is easy to ensure transparency even after the formation of a cured product (cured film), outdoor structures where the visibility of the base is particularly important, such as road signs, guide signs, billboards, electronic bulletin boards, traffic lights, It can be effectively applied to street lamps, lighthouses, and the like.

Examples of coating methods include spray coating, bar coating, spin coating, dispenser, sponge coating, brush coating, spatula coating, roller coating, and dipping. Among these, the spray coating method is preferred. In addition, the curable composition of the present invention does not require work such as wiping off, and is excellent in workability (coatability, paintability).

In addition, the coating amount (coating amount) of the curable composition may be appropriately adjusted according to the substrate, application, coating method, thickness of the cured film (average thickness), etc., and the weight after drying (formed after drying The weight of the cured product (cured film)) may be, for example, 0.1 to 80 g/m ² , preferably 5 to 40 g/m ² , more preferably 10 to 20 g/m ² . The number of times of coating may be one, or may be repeated so as to obtain a desired average thickness, for example. If the post-drying weight (weight as a cured product) is too large, the workability (coatability, paintability) may decrease, the weather resistance may decrease (for example, cracks may easily occur), and the base may be damaged. Conversely, if the amount is too small, white blurring may occur depending on the base material, resulting in reduced visibility, reduced durability and mechanical strength, and damage (or impact). There is also a possibility that resistance to such as may decrease.

In the present invention, the coated composition may be cured by standing (standing) together with the substrate at room temperature (for example, 20 to 30° C., preferably about 23° C.). The humidity at the time of leaving may be, for example, 10 to 90% RH (eg, 30 to 70% RH), preferably 40 to 60% RH (eg, about 50% RH). The time for standing is not particularly limited as long as the solvent (D) etc. is distilled off (removed) and a cured product can be formed. for example, 10 hours or longer), more preferably about 10 to 50 hours. When the silicone-based resin component (A), the reactive silicone-based oil component (B), the curing catalyst (C), etc. have an alkoxy group, the alcohol produced as a by-product when the curing reaction proceeds when left at room temperature is , may be removed (distilled off) during this time.

The curable composition of the present invention may be a room temperature curing type, but if necessary, it is heated (for example, further heat curing is performed after room temperature curing), or heat curing is performed instead of room temperature curing. may The heating temperature is not particularly limited, and may be 50° C. or higher (for example, about 50 to 120° C.). Heating can further improve the hardness of the cured product.

Since the surface of the cured product (or cured film) obtained in this way exhibits excellent snow and ice falling properties, snow is attached to the surface of the cured product, and the temperature is raised from -15 ° C. to 8 to 10 ° C. over 30 minutes. However, the time required for the snow to fall when the temperature is maintained at 8 to 10 ° C. is based on the base material (untreated base material that did not form a cured film) [e.g., metal base materials such as A5052 aluminum alloy plate, polymethyl methacrylate plate resin base material, etc.] may be shorter than the time required for the snow adhered to the surface to fall. The specific snow-falling time on the cured film surface of the present invention is, for example, 0.5 minutes or more (for example, 1 to 30 minutes) than when snow is attached to the untreated substrate (for example, A5052 aluminum alloy plate) surface. ), preferably 3 minutes or more (for example, 5 to 15 minutes), more preferably about 8 minutes or more. In the present specification and claims, the snow/ice-removal property (snow-removal time) can be measured by the method described in the snow-removal test in Examples described later.

In addition, since the cured product (or cured film) surface exhibits excellent water repellency, the water contact angle on the cured product surface may be, for example, about 70 ° or more (eg, 80 to 130 °), preferably 90 to It may be about 120° (eg, 100 to 110°). In the present specification and claims, the water contact angle on the surface of the cured product can be measured by the method described in the water repellency test in Examples described later.

Furthermore, the surface of the cured product (or cured film) can also exhibit excellent water slipperiness. The water sliding angle on the surface of the cured product may be, for example, about 0 to 40° or less (eg, 35° or less), preferably 30° or less (eg, 1 to 30°), more preferably 25° or less, particularly 20°. or less (for example, 5 to 10°). In the present specification and claims, the water sliding angle of the surface of the cured product can be measured by the method described in the water slipping test in Examples described later.

In addition, since the curable composition is excellent in workability (coatability, paintability), it is possible to form a coating film (cured film) with a good appearance, for example, without cracks and / or blurring, and various substrates. Even when applied to materials, it is easy to ensure the visibility of the base with a good appearance, and even if it is applied by various methods such as sponge coating and brush coating, it is possible to easily or efficiently form a coating film that suppresses paint marks and repelling. can.

In addition, the surface of the cured product (or cured film) can exhibit excellent durability (weather resistance or light resistance). Therefore, even after 480 hours of the accelerated weather resistance test according to JIS K 5600 7-7 (general test method for paint) (accelerated weather resistance and accelerated light resistance, xenon lamp method), the properties before the test, such as the above-mentioned cured product Properties such as water sliding angle and coating film appearance on the surface can be effectively maintained. In the present specification and claims, the accelerated light resistance test of the surface of the cured product can be measured by the method described in Examples below.

When the cured product forms a cured film, the cured film may have an average thickness of, for example, 1 to 80 μm (eg, 5 to 20 μm), preferably about 10 to 15 μm. If the average thickness is too thick, workability (coatability, paintability) may decrease, weather resistance may decrease (for example, cracks may occur easily), and the visibility of the base may decrease. Conversely, if it is too thin, depending on the base material, it may blur and visibility may decrease, durability and mechanical strength may decrease, and resistance to scratches (or impacts) may also decrease. be.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples. Details of raw materials used and evaluation methods are shown below.

[raw materials used]
(A) Silicone resin component KR-500: methyl-based silicone methoxy oligomer, composed of T units, kinematic viscosity at 25°C of 25 mm ² /s, manufactured by Shin-Etsu Chemical Co., Ltd. KR-400: methyl-based silicone methoxy oligomer, T (contains 10% by mass of organoaluminum-based catalyst DX-9740), kinematic viscosity at 25° C. 1.2 mm ² /s, manufactured by Shin-Etsu Chemical Co., Ltd. KC-89S: methyl-based silicone methoxy oligomer, T unit Composition, kinematic viscosity at 25° C. 5 mm ² /s, Shin-Etsu Chemical Co., Ltd. X-40-9225: Methyl-based silicone methoxy oligomer, composed of T units, kinematic viscosity at 25° C. 100 mm ² /s, Shin-Etsu Chemical ( Co., Ltd. X-40-9246: methyl-based silicone methoxy oligomer, composed of T units and D units, kinematic viscosity at 25° C. 80 mm ² /s, Shin-Etsu Chemical Co., Ltd. X-40-9250: methyl-based silicone Methoxy oligomer, composed of T units and D units, kinematic viscosity at 25°C of 80 mm ² /s, manufactured by Shin-Etsu Chemical Co., Ltd. (B) Silicone oil component KR-4000A: One end alkoxy-modified, kinematic viscosity at 25°C 60 mm ² /s, Shin-Etsu Chemical Co., Ltd. KP-983: one end alkoxy-modified, kinematic viscosity at 25° C. 23 mm ² /s, Shin-Etsu Chemical Co., Ltd. X-22-176DX: one end diol-modified, 25 Kinematic viscosity at ° C. 126 mm ² /s, manufactured by Shin-Etsu Chemical Co., Ltd. KF-96-1000cs: Non-reactive silicone oil (polydimethylsiloxane), kinematic viscosity at 25 ° C. 1000 mm ² /s, manufactured by Shin-Etsu Chemical Co., Ltd. (C) Curing catalyst D-25: Titanium-based (titanium (IV) tetra-n-butoxide), manufactured by Shin-Etsu Chemical Co., Ltd. Orgatics TC-401: Titanium-based chelate (titanium (IV) tetraacetylacetonate), 65 Mass% 2-propanol solution, manufactured by Matsumoto Fine Chemical Co., Ltd. DX-9740: Aluminum-based, manufactured by Shin-Etsu Chemical Co., Ltd. (D) Solvent 2-propanol (IPA): Vapor pressure at 20 ° C. 4 kPa, Kanto Chemical Co., Ltd. Made by ISOPAR-E: isoparaffinic solvent, vapor pressure at 20 ° 2.37 kPa, manufactured by ExxonMobil

[Preparation of curable composition]
In a 200 mL glass container, the silicone resin component (A), the silicone oil component (B), the curing catalyst (C) and the solvent (D) were blended at the mass ratios shown in each table (Tables 2 to 6) described later. , and stirred for 10 minutes using a magnetic stirrer to prepare a curable composition.

[Preparation of test piece]
A flat test piece (dimensions: 150 mm×70 mm, thickness: 2 mm, material: polymethyl methacrylate resin plate, polycarbonate resin plate and A5052 aluminum alloy plate) was used as the object (substrate). One surface of this flat test piece was treated with a primer according to each material. On this treated surface, the curable composition was applied with an air spray (“W-101-101E” manufactured by Anest Iwata Co., Ltd.) so that the weight after drying was 10 to 15 g/m ² . ° C.) and a humidity of 50% RH for 24 hours to prepare a test piece having a dry film (cured film) with a thickness of 10 to 15 μm.

[Evaluation method of cured film]
(Snow falling test (using shaved ice))
Using pure water (deionized water) and an electric ice shaver (“YSIA-F25” manufactured by Yamazen Co., Ltd.), shaved ice was prepared assuming wet snow. Under the condition of -15°C or less, 0.15 to 0.30 g/cm ² of the shaved ice was piled up on a horizontal test piece (substrate: A5052 aluminum alloy plate) using a sieve (5 mm opening). After standing at about -15°C for 5 minutes, the test piece was tilted at 90° (perpendicular to the ground). The temperature was gradually raised from −15° C. to about 8 to 10° C. in 30 minutes, and when the temperature was maintained at 8 to 10° C., snow falling (shaved ice falling) from the test piece was observed. Compared with an untreated substrate (untreated A5052 aluminum alloy plate) to which the curable composition was not applied (formed a cured film), it was judged that snow and ice falling quickly was superior.

◯: The timing of snow falling is earlier than that of the untreated base material. △: The timing of snow falling is the same as that of the untreated base material. ×: The timing of snow falling is later than that of the untreated base material.

(Water repellency test)
A contact angle meter ("OCA 15EC" manufactured by dataphysics instruments GmbH) was used to measure the contact angle of pure water (deionized water). A test piece was placed on a sample table so that the dry film (cured film) was horizontal, a 3 μL water droplet was dropped on the surface of the dry film, and the water contact angle of the water droplet was measured with a contact angle meter. The average value of three measurements was taken as the value of the contact angle. A water contact angle of 90° or more was judged to be excellent in water repellency. As the test piece, a test piece having a polymethyl methacrylate resin plate or a polycarbonate resin plate as a base material was used.

○: contact angle of water 90° or more △: contact angle of water 70° to less than 90° ×: contact angle of water less than 70°.

(Water sliding test)
A sliding angle of pure water (deionized water) was measured using a contact angle meter (“OCA 15EC” manufactured by dataphysics instruments GmbH). Place the test piece on the sample table so that the dry film (cured film) is horizontal, drop 50 μL of water droplets on the surface of the dry film, and gradually tilt the sample table until the water droplets start to slide. The angle (sliding angle) was measured. The average value of three measurements was taken as the value of the sliding angle. Water sliding angle of 25° or less was judged to be excellent in water sliding. As the test piece, a test piece having a polymethyl methacrylate resin plate or a polycarbonate resin plate as a base material was used.

〇 : Sliding angle of 25° or less △ : Sliding angle of over 25° and 40° or less × : Sliding angle of over 40° and 90° or less (water droplets fall)
XX: Water droplets do not drop even if the test piece is tilted at 90°.

(Appearance of coating film)
The dried film (cured film) of the test piece was visually observed and evaluated according to the following criteria. In addition, the dry film (cured film) of each test piece prepared using three types of base materials (polymethyl methacrylate resin plate, polycarbonate resin plate and A5052 aluminum alloy plate) was observed, and among them, the lowest evaluation ( The results of the test pieces with poor appearance) are described in each table (Tables 2 to 6) described later.

〇: No cracks or dullness on the dry film △: There are either cracks or dullness on the dry film ×: There are both cracks and dullness on the dry film ××: Not dry to the touch .

(Accelerated weather resistance test)
Using a “Super Xenon Weather Meter” manufactured by Suga Test Instruments Co., Ltd., the conditions for the accelerated weather resistance test conform to JIS K 5600 7-7 general paint test methods (accelerated weather resistance and accelerated light resistance, xenon lamp method). Then, an accelerated weathering test was performed on the specimen. A test piece having a polymethyl methacrylate resin plate as a base material was used as the test piece. Using the obtained test piece after 480 hours of the accelerated weather resistance test, the test was performed according to the same method and evaluation criteria as in the above sections (Water sliding test) and (Appearance of coating film) to evaluate weather resistance.

[Method for evaluating coating film of silicone oil component (B)]
A composition (diluted solution) is prepared by mixing 1 part by mass of the reactive silicone oil component (B) described above and 99 parts by mass of an isoparaffin solvent ("ISOPAR-E" manufactured by ExxonMobil). The resulting composition was applied to a smooth polycarbonate resin substrate (JIS K 6735 compliant) using a sponge so as to be 10 g/m ² (weight before drying), and was placed in an atmosphere of room temperature (23°C) and humidity of 50% RH. A specimen with a dry film (dry matter) on one side was prepared by standing under the surface for 24 hours. The water contact angle and water sliding angle of the obtained dry film were evaluated by the same methods as the above (water repellency test) and (water sliding test).

Table 1 below shows the evaluation results of the dry film (coating film) of the silicone oil component (B).

[Examples 1-1 to 1-4 and Reference Examples 1-1 to 1-2]
A curable composition was prepared at the mass ratio shown in Table 2 below, and a test piece was produced using the obtained curable composition. The compounding ratio and evaluation results of the curable composition are shown below.

Unless otherwise specified, "(A)/total" in the table indicates the mass ratio of silicone resin component (A) to the entire curable composition (total amount of components (A) to (D)). , "((A) + (B) + (C)) / total" is the mass ratio of the total amount of components (A) to (C) with respect to the entire curable composition [components that form a cured film (solvent solid content) concentration] (the same applies to the following tables). In addition, the numerical values in parentheses in Example 1-2 are 90.00 parts by mass of KR-400 100.00 parts by mass of methyl-based silicone methoxy oligomer as component (A), and 10.00 parts by mass of organic It means a value calculated using the aluminum-based catalyst DX-9740 as component (C).

As is clear from the results in Table 2, the examples (examples of the silicone-based resin component (A) formed with T units) were excellent in snow/ice falling properties, water repellency, water sliding properties, appearance, and weather resistance. . In addition, the test pieces of any of the examples were excellent in the visibility of the substrate. On the other hand, the reference examples (examples of the silicone-based resin component (A) containing the D unit) had good water repellency and appearance, but were inferior in snow and ice removal properties and water sliding properties.

[Examples 2-1 to 2-3 and Reference Examples 2-1 to 2-2]
A curable composition was prepared at the mass ratio shown in Table 3 below, and a test piece was produced using the obtained curable composition. The compounding ratio and evaluation results of the curable composition are shown below.

As is clear from the results in Table 3, the examples (examples of one-end-modified silicone oil component (B)) were excellent in snow and ice removal properties, water repellency, water slippage, and appearance. In addition, the test pieces of any of the examples were excellent in the visibility of the substrate. Weather resistance was low in Example 2-3 (an example of silicone oil component (B) modified with a diol at one end).

On the other hand, Reference Example 2-1 (an example of the unmodified silicone-based oil component (B)) exhibited excellent water repellency, but poor snow/ice and water slip properties. Therefore, it was found that high water repellency does not necessarily mean excellent snow and ice falling properties.

In addition, in Reference Example 2-2 (an example corresponding to the components of the curable composition described in Patent Document 2 and their proportions), the water repellency was excellent and the water slipperiness was also superior to that of Reference Example 2-1. Snow and ice resistance was low. Therefore, the non-tackiness of the cured film described in Patent Document 2 seems to have little effect on the snow/ice falling properties.

In addition, in the snow falling test of Example 2-1 (1-1), the snow fell about 10 minutes earlier than the untreated substrate (A5052 aluminum alloy plate). In addition, the test piece for the snow drop test (substrate: A5052 aluminum alloy plate) was tested in the same manner except that the test piece was changed to a test piece using a polymethyl methacrylate plate as a base material. In all of -1) to 2-3, the snow fell faster than the untreated polymethyl methacrylate plate (it was evaluated as ◯).

[Examples 3-1 to 3-8 and Reference Example 3-1]
A curable composition was prepared at the mass ratio shown in Table 4 below, and a test piece was produced using the obtained curable composition. The compounding ratio and evaluation results of the curable composition are shown below.

As is clear from the results in Table 4, the examples exhibited excellent snow/ice removal properties and water repellency even when the ratio of the one-end-modified silicone oil component (B) was changed within a predetermined range. On the other hand, in Reference Example 3-1, in which the proportion of the silicone-based oil component (B) is small, the water repellency was maintained, but the snow and ice falling properties were deteriorated.

Among Examples 3-1 to 3-6, in Example 3-6, cissing easily occurred during coating, probably because the amount of the silicone oil component (B) for enhancing water repellency was too large, and the appearance due to delustering. Unlike Examples 3-1 to 3-5, the workability (coatability, paintability) and the visibility of the base (appearance) were slightly deteriorated. In addition, repelling tended to occur more easily as the proportion of the component (B) increased. For example, when sponge coating was applied instead of spray coating, repelling did not occur in Example 3-3, but repelling occurred in Example 3-4.

Even if the type of the silicone-based resin component (A) in Examples 3-1 to 3-6 was changed, each property [snow/ice falling property, water repellency, water sliding property, coating film appearance, weather resistance and workability ( For example, there was no difference in the difficulty of repelling)]. That is, instead of KR-500 (100 parts by mass) in Examples 3-1 to 3-6, KR-400, KC-89S or X-40-9225 (100 parts by mass in any case) was used. , All of the above characteristics were similar to Examples 3-1 to 3-6 (In addition, in the example using KR-400, the curing catalyst in Examples 3-1 to 3-6 (prepared as in Table 2) without the addition of D-25 as

[Examples 4-1 to 4-8 and Reference Examples 4-1 to 4-2]
A curable composition was prepared at the mass ratio shown in Table 5 below, and a test piece was produced using the obtained curable composition. The compounding ratio and evaluation results of the curable composition are shown below. The values in parentheses in Examples 4-6 and 4-8 mean values calculated with the solid content of TC-401 as component (C).

As is clear from the results in Table 5, snow/ice falling properties and water repellency were excellent in all Examples, regardless of the type of curing catalyst. In addition, the test pieces of any of the examples were excellent in the visibility of the substrate.

From Reference Example 4-1, when the proportion of the curing catalyst (C) was small, it was not possible to cure at room temperature, and even though it was heated to about 100 ° C., a cured film could not be formed. Although slightly lower than those of Examples 4-2 and 4-3, all of the snow/ice removal properties, water repellency and appearance were good.

On the other hand, it was found from Reference Example 4-2 that when the proportion of the curing catalyst (C) was large, the snow/ice falling property and the water sliding property tended to decrease. In Example 4-4, although the water slippage was slightly lower than in Examples 4-2 and 4-3, all of the snow/ice removal properties, water repellency, and appearance were good. Defective appearance due to

Examples 4-7 and 4-8 are examples in which the type of solvent (D) was changed from Examples 4-3(1-1) and 4-6. All of Examples 4-7 and 4-8 had good snow/ice falling properties, water repellency, water sliding properties, appearance, weather resistance and visibility, and Examples 4-3 (1-1) and 4-6 and It was also excellent in workability (coatability, paintability).

[Examples 5-1 to 5-5]
A curable composition was prepared at the mass ratio shown in Table 6 below, and a test piece was produced using the obtained curable composition. The compounding ratio and evaluation results of the curable composition are shown below.

As is clear from the results in Table 6, the ratio of the total amount of components (A) to (C) to the entire curable composition (total amount of components (A) to (D)) (concentration of solids forming a cured film) Regardless, snow/ice removal, water repellency, and water sliding properties were excellent in all Examples.

In Example 5-1, depending on the test piece, it became whitish after drying, the luster (white blur) was observed, the visibility of the base was low, and the appearance was Δ. In addition, in Example 5-1, in order to obtain a predetermined post-drying weight (or film thickness), it was necessary to apply a larger amount than in other examples, and repelling tended to occur at that time. Workability (coatability, paintability) was low.

On the other hand, in Examples 5-2 to 5-5, all the test pieces had excellent base visibility, and workability in spray coating (coatability, paintability) was also good. If a sponge or a brush is used instead of the spray coating, the solid content concentration is too high in Example 5-5. The workability (coatability, paintability) and the visibility (appearance) of the base slightly decreased.

Since the cured product of the curable composition of the present invention has water repellency and snow and ice falling properties, it can be used as various coating compositions (coating compositions), particularly as a coating composition for snow damage countermeasures (for promoting snow and ice falling). It can be effectively used as a (snow and ice prevention or snow and ice fall promoting paint). In addition, since the curable composition of the present invention can be moisture-cured at room temperature, it is suitably used for applications that do not require heat treatment, and is also suitable for use in places where the use of fire is restricted.

In addition, the curable composition of the present invention is excellent in durability, and is therefore suitable for outdoor use and general household use. For this reason, snow and ice should not adhere to the surfaces of buildings, structures such as buildings, storage tanks, bridges, utility poles, traffic lights, cables, antennas, signs, etc., and transportation equipment such as automobiles, vehicles, ships, and aircraft. It can be used as a composition for prevention.

Specifically, it can be used as a composition for preventing snow and/or ice from adhering, in particular, as a composition for promoting snow and ice falling (snow and ice accelerating paint), for example, road signs, traffic lights ( LED traffic lights, etc.), ETC sensors, highway noise barriers, line switching machines, roofs, parabolic antennas, electric wires, bridges, weather measuring instruments (airflow meters), wind turbine blades, transportation equipment [automobiles (windows, wheels, Snowplow propellers, etc.), vehicles (railway car pantographs, etc.), ships, aircraft (plane blades, drones, etc.)], covers or housings used for transportation equipment [e.g., lights (or lamps), sensors, etc. It can be used as a surface protective film (snow and ice falling promotion film) for electric and electronic parts such as covers or housings of (vehicle sensors, railway vehicle speedometers, etc.).

Claims (14)

A curable composition comprising a silicone resin component (A) and a reactive silicone oil component (B) having at least one reactive group,
The silicone resin component (A) does not substantially contain D units,
A curable composition in which the proportion of the reactive silicone oil component (B) is 0.03 to 10 parts by mass per 100 parts by mass of the silicone resin component (A). 2. The curable composition according to claim 1, wherein said reactive silicone oil component (B) has a reactive group only at one molecular end. 3. The curable composition according to claim 1, wherein said reactive groups are hydroxyl groups directly bonded to silicon atoms and/or alkoxy groups directly bonded to silicon atoms. When the reactive silicone oil component (B) is a composition prepared under the following conditions (i) and a dry product is prepared on a smooth substrate, the surface of the dry product has the following characteristics (ii) and (iii). ), the curable composition according to any one of claims 1 to 3.
(i) A composition comprising 1 part by mass of the reactive silicone oil component (B) and 99 parts by mass of an isoparaffinic solvent (ii) A water contact angle of 90° or more when the amount of water dropped is 3 μL (iii) Water dropped Water sliding angle of 50 μL is 25 ° or less Further, a curing catalyst (C) is included, and the ratio of the curing catalyst (C) is 0.05 parts by mass or more and less than 20 parts by mass with respect to 100 parts by mass of the silicone resin component (A). 5. The curable composition according to any one of 4. Furthermore, it contains a curing catalyst (C) and a solvent (D), and the ratio of the total amount of the silicone resin component (A), the reactive silicone oil component (B) and the curing catalyst (C) is the curable composition The curable composition according to any one of claims 1 to 5, which is 9.5% by mass or more based on the entire product. The curable composition according to any one of claims 1 to 6, which is a coating composition for promoting snow and ice. It is hardened to form a hardened product, snow is attached to the surface of the resulting hardened product, and the time taken for the snow to fall when the temperature is raised from -15 ° C. to 8 to 10 ° C. over 30 minutes is the A5052 aluminum alloy plate surface. 8. A curable composition according to any one of claims 1 to 7, which is shorter than the time it takes for snow deposited on the surface to fall. A cured product of the curable composition according to any one of claims 1 to 8. A method for producing a cured product by coating the surface of a substrate with the curable composition according to any one of claims 1 to 8 and curing the resulting coating film. A composite comprising a base material and a cured film covering the surface of the base material and formed of the cured product according to claim 9 . 12. The composite of Claim 11, wherein the substrate is a substrate forming at least a partial region of an outdoor structure. 13. The composite according to claim 12, wherein said outdoor structure is a road sign, guide sign, billboard, electronic bulletin board, traffic light, street light or lighthouse. A method of coating the surface of a substrate with the curable composition according to any one of claims 1 to 8 to form a cured film, thereby promoting snow and ice falling on the surface of the substrate.